This application relates to a method for imparting fire-retardant properties to polycarbonate resins, to compositions useful in the method, and to fire-retarded polycarbonate resins of the type produced by the method. The fire-retarded polycarbonates are suitably used to make molded articles, particularly thin-walled articles.
Because of their strength and clarity, polycarbonate resins have a great many significant commercial applications. Unfortunately, polycarbonate resins are inherently flammable and can drip hot molten material causing nearby materials to catch fire as well. Thus, in order to safely utilize polycarbonates in many applications it is necessary to include additives which retard the flammability of the material and/or which reduce dripping. The challenge is to identify additives which accomplish this purpose without compromising the desirable properties of strength and clarity, without introducing new problems (such as the potential environmental problems associated with some halogenated additives) and without prohibitively increasing the price.
A variety of different materials have been described for use in producing fire-retarded and/or drip-resistant polycarbonates. Exemplary of these are the materials described in U.S. Pat. Nos. 3,971,756, 4,028,297, 4,110,299, 4,130,530 4,303,575, 4,335,038, 4,552,911, 4,916,194, 5,218,027 and 5,508,323. Notwithstanding these varied disclosures, however, there remains room for improvement in the formulation of firepolycarbonate resin.
Among the additives which are widely used commercially in fire-retarded polycarbonate resin compositions are organic salts, particularly sulfonic acid salts. Particular examples of these salts are perfluoroalkane sulfonates, such as potassium perfluorobutane sulfonate (xe2x80x9cKPFBSxe2x80x9d, also known as xe2x80x9cRimar saltxe2x80x9d) and potassium diphenylsulfone sulfonate (xe2x80x9cKSSxe2x80x9d) yield haze free compositions when blended with polycarbonate resin. The use of perfluoroalkane sulfonates in polycarbonate resins is described in U.S. Pat. No. 3,775,367. However, the benefits which can be obtained using these materials alone are limited and indeed additional additives are generally included. The conventional means for enhancing the fire-retardant properties of these type of compositions while retaining transparency has been the addition of soluble organic halogen additives. For example, commercial grades of LEXAN polycarbonate resin (eg. 940A, 920A) contain a combination of KSS (0.3 phr) and a tetrabromo-bisphenol/bisphenol A copolymer (0.5 phr, net 0.13 phr bromine content). Without the bromine, the 920A and 940A grades have inconsistent/unreliable performance in the UL94 VO 125 mil flammability test that these grades are designed to meet. However, the brominatedadditive is unsuitable for compositions which are required to meet xe2x80x9cECOs-friendlyxe2x80x9d tandards, since these standards prohibit the inclusion of bromine or chlorine based FR additives
U.S. Pat. No. 3,933,734 discloses the use of monomeric or polymeric aromatic sulfonates or mixtures thereof as fire-retardant additives for polycarbonates. U.S. Pat. No. 6,353,046 issued Mar. 5, 2002 discloses that improved fireproperties can be imparted to polycarbonate resin composition by incorporating into the polycarbonate a firecomponent comprising a perfluoroalkane sulfonate, such as potassium perfluorobutane sulfonate, and a cyclic siloxane, such as octaphenylcyclotetrasiloxane.
It has now been surprisingly found that a combination of a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid act synergistically at low levels in polycabobnate compositions with high melt strength to provide flame-retarded polycarbonate compositions. Thus, the present invention provides a method for making a flame-retarded polycarbonate resin comprising adding to the high melt-strength polycarbonate resin an effective flame-retardant amount of a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid. Where appropriate, the melt strength of the polycarbonate is enhanced by the addition of an antidrip agent. The two salts may be formulated in advance into a composition in accordance with the invention. Use of such a composition, particularly in an aqueous carrier, results in superior fire-retardant performance.
The present invention provides a method for making a flame-retarded polycarbonate resin by adding to a high melt strength polycarbonate resin (for example produced by addition of an antidrip) an effective flame-retardant amount of a potassium salt of a perfluoroalkane sulfonate, aand sodium salt of toluene sulfonic acid. In a further aspect, the present invention provides a high melt strength polycarbonate resin composition with flame-retarded properties. The composition comprises a high melt strength polycarbonate resin and an effective flame-retardant amount of a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid. In still a further aspect, the invention provides a flame-retardant composition comprising a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid in a ratio which provides synergistic effectiveness as a flame-retardant additive for polycarbonate.
The polycarbonate resin used in the method and composition of the invention may be of any grade and made by any method. Thus, for example, the polycarbonate may be made via interfacial processes or by melt process (catalytic transesterification). The polycarbonate may be either branched or linear in structure, and may include functional substituents. Polycarbonate copolymers are also included within the invention. Techniques for manufacture of polycarbonates by these processes are well known, for example from U.S. Pat. Nos. 3,030,331, 3,169,121, 4,130,548, 4,286,083, 4,552,704, 5,210,268 and 5,606,007. The polycarbonate is one which can be characterized as having high melt strength, i.e. a melt strength of at least R*=1.8. R* is the viscosity ratio at 1 rad/s and at 100 rad/s measured at a temperature when the viscosity at 100 rad/s is equal to 20,000 poise. High melt strength can be an inherent property of the polycarbonate, for example as a result of a branched polycarbonate structure, or can be achieved through the addition of an antidrip agent.
The potassium salt of a perfluoroalkane sulfonate is preferably one having a to 4 carbon atoms in the alkane group. Specific, non-limiting examples of suitable compounds are potassium perfluorobutane sulfonate and potassium trifluoromethane sulfonate. The sodium salt of toluene sulfonic acid is preferably sodium toluene sulfonic acid.
In an embodiment of the method of the invention, the potassium salt of perfluoroalkane sulfonate and the sodium salt of the toluene sulfonic acid are blended with molten polycarbonate, for example in a screwe-type xtruder, and extruded and molded into parts of desired shapes. They may be added to the polycarbonate in combination, for example as a fireadditive composition comprising a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid, or sequentially in either order.
The potassium salt of the perfluoroalkane sulfonate and the sodium salt of the toluene sulfonic acid are combined with the polycarbonate resin in an effective flame-retardant amount. An effective, flame-retardant amount is one that increases the flame-resistant properties of the polycarbonate, as compared to an otherwise identical composition without the salts of a perfluoroalkane sulfonate and a toluene sulfonic acid. While the specific method for testing for flame-retardant properties is not critical, one common method that may be employed involves the formation of bars molded from extruded polycarbonate and tested using the standard Underwriters Laboratory UL 94 test method. The data may be analyzed by calculation of the average flame out time (avFOTsec), standard deviation of the flame out time (sdFOTsec) and the total number of drips, and using statistical methods to convert that data to a prediction of the probability of first time pass, or xe2x80x9cp(FTP)xe2x80x9d that a particular sample formulation would achieve a VO xe2x80x9cpassxe2x80x9d rating in the conventional UL94 testing of 5 bar.s Preferably p(FTP) will be as close to 1 as possible, for example greater than 0.9 and more preferably greater than 0.95, for maximum flamep-retardant erformance in UL Testing.
In the method and polycarbonate-containing compositions of the invention, the amount of postassium salt of perfluoroalkane sulfonate is suitably low, to minimize cost, for example in the range of 0.004 to 0.05 weight %, more preferably from 0.008 to 0.03 weight %. The amount of the sodium salt of the toluene sulfonic acid is suitably from 0.001 to 0.1 weight %, more preferably from 0.005 to 0.05 weight %. Particularly preferred are combinations of at least 0.009 weight % of the potassium metal salt of perfluoroalkane sulfonate and at least 0.005 weight % of the sodium salt of the toluene sulfonic acid, for example 0.001 to 0.05% of the potassium salt of the perfluoroalkane sulfonate and 0.005 to 0.2% sodium salt of the toluene sulfonic acid.
The fire-retarded polycarbonate resins of the invention may also include an antidrip agent. As used in the specification and claims of this application, the term xe2x80x9cantidripxe2x80x9d refers to an additive which increases the melt strength of the polycarbonate, thereby reducing the tendency of the resin, when heated to close to melting, to drip. Examples of suitable antidrip agents include PTFE-based antidrip agents, such as 1/1 dispersion of PTFE in styrene acrylonitrile resin, emulsion based PTFE, and steam-precipitated PTFE. The antidrip agent is added in an amount effective to increase the melt strength and reduce drip, for example in the range of from 0.05 to 0.5 weight %.
Other additives which are conventional in the art may also be added to the polycarbonate resin in the method and compositions of the invention. Such additives include but are not limited to stabilizers, mold release agents, light stabilizers, heat stabilizers, pigments, dyes, PTFE, glass fibers, and fillers.
Polycarbonate resin in accordance with the invention containing a fire-retardant comprising a potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid is suitably used for making molded articles. The polycarbonate is particularly suitable for making thin walled articles, for examples articles having a wall thickness of less than 1.5 mm, i.e., 1 mm to 1.5 mm, because of its ability to achieve good fire-retardance even for thin pieces of material. These articles may be formed by extrusion, or blow molding.
The fire-retardant additive in accordance with the invention suitably comprises potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid in a ratio which provides synergistic effectiveness as a flame-retardant additive for polycarbonate. For example, the composition suitably contains the potassium salt of a perfluoroalkane sulfonate and a sodium salt of toluene sulfonic acid in a ratio of from about 0.1 to 2.0 by weight, more preferably 0.18 to 1.8 by weight. This, composition is added to polycarbonate resin in an amount appropriate to achieve the levels of the individual additives described above.
The invention will now be further described with reference to the following non-limiting examples.